Lubricating composition containing an acylated nitrogen compound



United States Patent Office Fatented Sept. 13, 1966 3,272,746 LUBIRECATING COMPUSHIUN CUNTAHNING AN ACYLATED NITROGEN COMPQUND William M. Le Suer, Cleveland, and George R. Norman,

Lyndhurst, Uhio, assignors to The Lnbrizol Corporation, Wickiiiie, ()hio, a corporation of Qhio No Drawing. Filed Nov. 22, 1965, Ser. No. 509,172 18 Claims. (Cl. 252-475) This is a continuation-in-part of copending application Serial No. 126,809 filed July 21, 1961, now U.S. 3,219,666 which was a continuation-in-part of application Serial No. 802,667 filed March 30, 1959, now U.S. 3,172,892. This application is also a continuation-in-part of copending application Serial No. 437,547 filed March 5, 1965, now abandoned and copending application Serial No. 468,948 filed July 1, 1965.

This invention relates to oil-soluble nitrogen-containing compositions and to the process of preparing the same. The compositions of this invention are useful as dispersing agents in lubricants, especially lubricants intended for use in the crankcase of internal combustion engines, gears, and power transmitting units.

One of the principal problems associated with present day crankcase lubricants is that posed by the inevitable presence in the lubricant of foreign particles such as dirt, soot, water and decomposition products resulting from breakdown of the lubricating oil. Even if there were none of this latter contaminant present the very nature of the design of the modern internal combustion engine is such that a significant amount of foreign matter will accumulate in the crankcase. Perhaps the most important of these contaminants is water because it seems to be responsible for the deposition of a mayonnaise-like sludge. It appears that if there were no water present the solid components of the mayonnaise-like sludge would circulate with the oil and be removed by the oil filter. It will be readily appreciated that the deposition of the sludge presents a serious problem with respect to the eflicient operation of the engine and that it is desirable to prevent such deposition of sludge-like material.

The presence of water and the precursors of sludge in a lubricating oil is dependent largely upon the operating temperature of the oil. If the oil is operated at a high temperature the water, of course, will be eliminated by evaporation about as fast as it accumulates. In the absence of water as stated above the other foreign particles will be removed by the filter. At low oil temperatures, on the other hand, water will accumulate and so consequently will sludge. It is apparent that the environment in which a crankcase lubricant is maintained will determine to a large extent the ultimate performance of that lubricant.

High operating temperatures are characteristic of a lubricant in an engine that is run at relatively constant high speed. Thus, in an engine that is run at 60 miles per hours for a long period of time it is very unlikely that there will be any accumulation of water and it is similarly unlikely that there will be any formation and deposition of sludge, but in ordinary stop-and-go driving such as is the case with taxicabs, delivery trucks, police cruisers, etc., the crankcase lubricant will be alternately hot and cold, an ideal environment for the accumulation of water. In such cases the formation of sludge is a serious problem. This problem has been with the automotive industry for many years and its solution has been approached by the use of known detergents such as metal phenates and sulfonates but without notable success. Although such known detergents are very effective in solving the detergency problems associated with motor oils at high temperatures they have not been particularly effective in solving the problems associated with low temperature operation or, to put it better, those problems which are associated with crankcase lubricants in engines which are operated at alternating high and low temperatures.

It is accordingly, a principal object of this invention to provide novel compositions of matter.

It is also an object of this invention to provide compositions which are adapted for use as additives in hydrocarbon oils.

It is also an object of this invention to provide compositions which are effective as detergents in lubricating compositions.

It is another object of this invention to provide a novel process for the preparation of products which are effective as dispersants in lubricant compositions.

It is another object of this invention to provide novel compositions which are effective dispersants in lubricant compositions intended for use in engines operated at alternating high and low temperatures.

It is another object of this invention to provide improvide hydrocarbon oil compositions.

It is another object of this invention to provide improved lubricating compositions.

It is another object of this invention to provide improved fuel compositions.

These and other objects are achieved in accordance with this invention by providing a detergent composition comprising an oil-soluble, acylated nitrogen composition characterized by the presence Within its structure of (A) a hydrocarbon-substituted polar group selected from the class consisting of acyl, acylimidoyl, and acyloxy radicals wherein the substantially hydrocarbon substituent contains at least about 50 aliphatic carbon atoms and (B) a nitrogen-containing group characterized by a nitrogen atom attached directly to said relatively polar group.

A critical aspect of this invention is the size of the hydrocarbon substituent in the acylated nitrogen compounds. Thus, only acylated nitrogen compositions having at least about 50 aliphatic carbon atoms in the hydrocarbon substituent are contemplated as being within the scope of this invention. Furthermore, in the case of acylated nitrogen compositions having two or more polar groups in a molecule, the hydrocarbon substituent must then contain at least about 25 aliphatic carbon atoms per each polar group. This lower limit is based not only upon the consideration of the oilsolubility of the acylated nitrogen compositions but also upon the effectiveness of such compounds as additives in hydrocarbon oils for the purposes of this invention. It has now been discovered that while acylated nitrogen compositions having less than the minimum number of such aliphatic carbon atoms may be sufi iciently oil-soluble, they nevertheless are not sufficiently effective to be useful as additives of this invention. Furthermore, it has been discovered that their effectiveness diminishes sharply with a corresponding decrease in the size of the hydrocarbon substituent so that acylated nitrogen compositions having less than about 35 aliphatic car-hon atoms in such substituent either are ineffective or produce detrimental results when added to a hydrocarbon oil.

Another important aspect of this invention is the structural constitution of the hydrocarbon substituent. Thus, the radical preferably should be substantially saturated, i.e., at least about of the total number of carbonto-carbon covalent linkages are saturated linkages. An excessive proportion of unsaturated linkages renders the molecule susceptible to oxidation, degradation, and polymerization and results in products unsuitable for use in hydrocarbon oils in many applications.

The hydrocarbon substituent of the acylated nitro gen compositions of this invention preferably should be substantially free from large oil-solubilizing pendant groups, i.e., groups having more than about 6 aliphatic carbon atoms. While some large oil-solubilizing pendant groups may be present, they preferably should be present in proportions less than about one such group for every 25 aliphatic carbon atoms in the main hydrocarbon chain. A higher proportion of large pendant groups impairs the effectiveness of the acylated nitrogen compositions of this invention as additives in hydrocarbon oils.

The hydrocarbon substituent may contain polar substituents provided, however, that the polar substituents are not present in proportions sufficiently large to alter significantly the hydrocarbon character of the radical. The polar substituents are exemplified by chloro, bromo, keto, ethereal, aldehydro, nitro, etc. The upper limit with respect to the proportion of such polar substituents in the radical is approximately based on the weight of the hydrocarbon portion of the radical.

The sources of the hydrocarbon substituent include principally the high molecular weight substantially saturated petroleum fractions and substantially saturated olefin polymers, particularly polymers of mono-olefins having from 2 to about 30 carbon atoms. The especially useful polymers are the polymers of l-monoolefins such as ethylene, propene, l-butene, isobutene, I-hexene, l-octene, 2-methyl-1-heptene, 3-cyclohexyl-1- butene, and 2-methyl-5-propyl-l-hexene. Polymers of medial olefins, i.e., olefins in which the olefinic linkage is not at the terminal position, likewise are useful. They are illustrated by Z-butene, 3-pentene, and 4-octene.

Also useful are the interpolymers of the olefins such as those illustrated above with other interpolymerizable olefinic substances such as aromatic olefins, cyclic olefins, and polyolefins. Such interpolymers include, for example, those prepared "by polymerizing isobutene with styrene; isobutene with butadiene; propene with isoprene; ethylene with piperylene; isobutene with chloroprene; isobutene with p-methyl styrene; l-hexene with 1,3-hexadiene; l-octene with l-hexene; I-heptene with l-pentene, 3-methyl-1-butene with l-octene; 3,3-dimethyl-l-pentene with l-hexene; isobutene with styrene and piperylene; etc.

The relative proportions of the mono-olefins to the other monomers in the interpolymers influence the stability and oil-solubility of the final acylated nitrogen compositions derived from such interpolymers. Thus, for reasons of oil-solubility and stability the interpolymers contemplated for use in this invention should be substantially aliphatic and substantially saturated, i.e., they should contain at least about 80%, preferably at least about 95%, on a weight basis of units derived from the aliphatic mono-olefins and no more than about 5% of olefinic linkages based on the total number of carbon-to-carbon covalent linkages. In most instances, the percentage of olefinic linkages should be less than about 2% of the total number of carbon-tocarbon covalent linkages.

Specific examples of such interpolymers include copolymer of 95% (by weight) of isobutene with 5% of styrene; terpolymer of 98% of isobutene with 1% of piperylene and 1% of chloroprene; terpolymer of 95% of isobutene with 2% of 1-butene and 3% of l-hexene; terpolymer of 60% of isobutene with of l-pentene and 20% of l-octene; copolymer of 80% of l-hexene and 20% of l-heptene; terpolymer of 90% of isobutene with 2% of cyclohexene and 8% of propene; and copolymer of 80% of ethylene and 20% of propene.

Another source of the substantially hydrocarbon radical comprises saturated aliphatic hydrocarbons such as highly refined high molecular weight white oils or synthetic alkanes such as are obtained by hydrogenation of high molecular weight olefin polymers illustrated above or high molectular weight olefinic substances.

The use of olefin polymers having molecular weights of about 7505000 is preferred. Higher molecular weight olefin polymers having molecular weights from about 10,000 to about 100,000 or higher have been found to impart also viscosity index improving properties to the acylated nitrogen compositions of this invention. In many instances the use of such higher molecular weight olefin polymers is desirable. On the other hand, olefin polymers having molecular weights less than about 700 are not useful.

The relatively polar group of the acylated nitrogen compositions is selected from the class consisting of acyl, acylimidoyl, and acyloxy radicals. These radicals have the following structural configurations, respectively:

NR2 R1("], R1(i7and Ri( JO- wherein R represents the substantially hydrocarbon substituent described hereinbefore and R represents a hydrogen radical or an organic radical such as a hydrocarbon radical or a polar-substituted hydrocarbon radical.

The nitrogen-containing group of the acylated nitrogen compositions of this invention is derived from compounds characterized by a radical having the structural configuration The two remaining valences of the nitrogen atom of the above radical preferably are satisfied by hydrogen, amino, or organic radicals bonded to said nitrogen atom through direct carbon-to-nitrogen linkages. Thus, the compounds from which the nitrogen-containing group may be derived include principally ammonia, aliphatic amines, aromatic amines, heterocyclic amines or carbocyclic amines. The amines may be primary or secondary amines and may also be polyamines such as alkylene amines, arylene amines, cyclic polyamines, and the hydroxy-substituted derivatives of such polyamines.

Specific amines of these types are methylamine, N- methylethylamine, N-methyl-octylamine, N-cyclohexylanaline, dibutylamine, cyclohexylamine, aniline, di(pmethylphenyl)amine, dodecylamine, octadecylamine, ophenylenediamine, N,N di-n-butyl-p-phenylenediamine, mor-pholine, piperazine, tetrahydropyr-azine, indole, hexahydro-1,3,5-triazine, 1-H-1,2,4-triazole, melamine, bis-(paminophenyl)methane, phenyl-methylenimine, menthanediamine, cyclohexamine, pyrrolidine, 3-amino-5,6-diphenyl-1,2,4 triazine, quinonediimine, 1,3 indandiimine, 2- octadecyl-imidazoline, 2 phenyl-4-methyl-imidazolidine, oxazolidine, ethanolamine, diethanolamine, and 2-heptyloxazolidine.

A preferred source of the nitrogen-containing group consists of polyamines, especially alkylene amines conforming for the most part to the formula HN alky1eue-N H l K i).

wherein n is an integer preferably less than about 10, A is a substantially hydrocarbon or hydrogen radical, and the alkylene radical is preferably a lower alkylene radical having less than about 8 carbon atoms. The alkylene amines include principally methylene amines, ethylene amines, butylene amines, propylene amines, pentylene amines, hexylene amines, heptylene amines, octylene amines, other polymethylene amines, and also the cyclic and the higher homologs of such amines such as piperazines and amino-alkyl-substituted piperazines. They are exemplified specifically by: ethylene diamine, triethylene.

tetramine, propylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene)tria-mine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pen-taethylene hexamine, di(trimethylene triamine, 2-heptyl-3- Z-aminopropyl irnidazoline, 4-methylimidazoline, 1,3 -bis (Z-aminoethyl imidazo- Iline, pyrimidine, 1-(2-aminopropyl)piperazine, l,4-bis(2- aminoethyl)piperazine, and 2-methyl-1-(2-aminobutyl) piperazine. High homologs such as are obtained by condensing two or more of the above illustrated alkylene amines likewise are useful.

The ethylene amines are especially useful. They are described in some detail under the heading Ethylene Amines in Encycylopedia of Chemical Technology Kirk and Othmer, volume 5, pages 898905, Interscience Publishers, New York (1950). Such compounds are prepared most conveniently by the reaction of an alkylene chloride with ammonia. The reaction results in the production of somewhat complex mixtures of alkylene amines, including cyclic condensation products such as piperazines. These mixtures find use in the process of this invention. On the other hand, quite satisfactory products may be obtained also by the use of pure alkylene amines. An especially useful alkylene amine for reasons of economy as well as effectiveness of the products derived therefrom is a mixture of ethylene amines prepared by the reaction of ethylene chloride and ammonia and having a composition which corresponds to that of tetraethylene pentamine.

Hydroxyalkyl-substituted alkylene amines, i.e., alkylene amines having one or more hydroxyalkyl substituents on the nitrogen atoms, likewise are contemplated for use herein. The hydroxyalkyl-substituted alkylene amines are preferably those in which the alkyl group is a lower alkyl group, i.e., having less than about 6 carbon atoms. Examples of such amines include N-(2-hydroxyethyl) ethylene diamine, N,N' bis(2 hydroxyethyl)ethylene diamine, 1-(Z-hydroxyethyl)piperazine, mono-hydroxypropyl-substituted diethylene triamine, 1,4-bis(2-hydroxypropyl) piperazine, di-hydroxypropyl-substituted tetraethylene pentamine, N-(3-hydroxypropyl)tetramethylene diamine, and 2-heptadecyl-1-(2-hy droxyethyl) imidazoline.

Higher homologs such as are obtained by condensation of the above-illustrated alkylene amines or hydroxy alkyl-substituted alkylene amines through amino radicals or through hydroxy radicals are likewise useful. It will be appreciated that condensation through amino radicals results in a higher amine accompanied with removal of ammonia and that condensation through the hydroxy radicals results in products containing ether linkages accompanied with removal of water.

Other sources of the nitrogen-containing group include ureas, thioureas, hydrazines, guanidines, amidines, amides, thioamides, cyanamides, etc. Specific examples illustrating such compounds are: hydrazine, phenylhydrazine, N, N'-diphenylhydrazine, octadecylhydrazine, benzoylhydrazine, urea, thiourea, N-butylurea, stearylamide, oleylamide, guanidine, 1,3-diphenylguanidine, 1,2,3-tributylguanidine, benzamidine, octadecamidine, N,N-dimethylstearamidine, cyanamide, dicyandiamide, guanylurea, aminoguanidine, etc.

As indicated previously, the nitrogen-containing group in the acylated nitrogen compositions of this invention is characterized by a nitrogen atom attached directly to the relatively polar group. It will be appreciated, of course, that the linkage between a nitrogen atom and an acyl radical is representative of an amide or an imide structure, that the linkage between a nitrogen atom and an acylimidoyl radical is representative of an amidine structure, and that the linkage between a nitrogen atom and an acyloxy radical is representative of an ammonium-carboxylic acid salt structure. Thus, the acylated nitrogen compositions of this invention are characterized. by amide, imide, amidine, or salt linkages and in many instances a mixture of such linkages. Those containing two such linkages separated by a lower alkylene radical (i.e., one having less than about 6 carbon atoms), such as are derived from succinic, glutaric, or adipic radicals, are especially preferred in this invention.

A convenient method for preparing the acylated nitrogen compositions of this invention comprises reacting a high molecular weight acid-producing compoundv characterized by the presence within its structure of a high molecular weight oil-solubilizing group having at least about 50 aliphatic carbon atoms and at least one acid-producing group having the structural configuration o ax wherein X is selected from the class consisting of halogen, hydroxy, hydrocarbon-oxy, acyloxy, and amino radicals derived from ammonia or a lower primary amine such as a mono-alkylamine or mono-arylamine having no more than about 6 aliphatic carbon atoms with at least about one-half an equivalent amount of a nitrogen-containing compound characterized by the presence within its structure of at least one radical having the structural configuration The above process involves a reaction between the acidproducing group with the nitrogen-containing radical to result in the direct attachment of the nitrogen atoms to a polar radical, i.e., acyl, acylimidoyl, or acyloxy radical derived from the acid-producing group. The linkage formed between the nitrogen atom and the polar radical may thus be that representative of a salt, amide, imide, or amidine radical. In most instances, the product of the above process contains a mixture of linkages representative of such radicals. The precise relative proportions of such radicals in the product usually are not known as they depend to a large measure upon the type of the acidproducing group and the nitrogen-containing radical involved in the reaction and also upon the environment (e.g., temperature) in which the reaction is carried out. To illustrate, the reaction involving an acid or an'hydride group with an amino nitrogen-containing radical at relatively low temperatures such as below about 60 C. results predominantly in a salt linkage (i.e.,

but at relatively high temperatures such as above about C. results predominantly in an amide, imide, or amidine linkage (i.e.,

0 ll ll -C--N 0r -CN) The products obtained by the above process, irrespective of the nature or relative proportions of the linkages present therein, have been found to be effective as additives in hydrocarbon oils for the purposes of this invention.

The acid-producing compounds contemplated for use in the above process include mono-carboxylic and polycarboxylic acids, acid halides, esters, and anhydrides as well as imides and amides derived from ammonia or a lower primary amine, and also mixtures of such compounds. The imide or amide of ammonia or a lower primary amine is especially useful for preparing the acylated nitrogen compositions having more than one nitrogencontaining radicals. The nature of the oil-solubilizing group in such compounds should be the same as that which characterized the hydrocarbon substituent, described previously, in the acylated nitrogen compositions of this invention.

The substantially saturated, aliphatic hydrocarbon-substituted succinic acids and anhydrides are especially preferred for use as the acid-producing reactant in this process for reasons of the particular effectiveness of the products obtained from such compounds as additives in hydrocarbon oils. The succinic compounds are readily available from the reaction of maleic anhydride with a high molecular Weight olefin or a chlorinated hydrocarbon such as the olefin polymer described hereinabove. The reaction involves merely heating the two reactants at a temperature about 100-200 C. The product from such a reaction is an alkenyl succinic anhydride. The alkenyl group may be hydrogenated to an alkyl group. The anhydride may be hydrolyzed by treatment with Water or steam to the corresponding acid. Either the anhydride or the acid may be converted to the corresponding acid halide or ester by reaction with, e.g., phosphorus halide, phenols or alcohols or to the corresponding imide or amide by reaction with ammonia or a lower primary amine.

In lieu of the high molecular Weight olefins or chlorinated hydrocarbons, other high molecular weight hydrocarbons containing an activating polar substituent, i.e., a substituent which is capable of activating the hydrocarbon molecule in respect to reaction with maleic acid or anhydride may be used in the above-illustrated reaction for preparing the succinic compounds. Such polar substituents may be illustrated by sulfide, disulfide, nitro, mercaptan, bromine, ketone, and aldehyde radicals. Examples of such polar-substituted hydrocarbons include polypr-opene sulfide, di-polyisobutene disulfide, nitrated mineral oil, di-polyethylene sulfide, brominated polyethylene, etc. Another method useful for preparing the succinic acids and anhydrides involves the reaction of itaconic acid with a high molecular weight olefin or a polar-substituted hydrocarbon at a, temperature usually within the range from about 100 C. to about 200 C.

The polycarboxylic acids and derivatives thereof having more than two carboxylic radicals per molecule which are contemplated for use in this invention are those containing at least about 50 aliphatic carbon atoms per molecule and furthermore, at least about 25 aliphatic carbon atoms per each carboxylic radical. Such acids may be prepared by halogenating a high molecular weight hydrocarbon such as the olefin polymer described hereinabove to produce a poly-halogenated product, converting the polyhalogenated product to a poly-nitrile, and then hydrolyzing the poly-nitrile. They maybe prepared also by oxidation of a high molecular weight polyhydric alcohol with potassium permanganate, nitric acid, or a like oxidizing agent. Another method for preparing such polycarboxylic acids involves the reaction of an olefin or a polarsubstituted hydrocarbon such as a chloro-polyisobutene with an unsaturated poly-carboxylic acid such as 2- pentene-1,3,5-tricarboxylic acid obtained by dehydration of citric acid.

The mono-carboxylic acids and derivatives thereof may be obtained by oxidizing a mono-hydric alcohol with potassium permanganate or by reacting a halogenated high molecular olefin polymer with a ketene. Another convenient method for preparing the monocarboxylic acids involves the reaction of metallic sodium with an acetoacetic ester or a malonic ester of an alkanol to form a sodium derivative of the ester and the subsequent reaction of the sodium derivative with a halogenated high molecular weight hydrocarbon such as brominated wax or brominated polyisobutene. Other methods include the reaction of a high molecular weight olefin with ozone; the Haloform Reaction; the reaction of an organometallic complex (such as lithium-olefin complex) with carbon dioxide; the reaction of a chlorinated hydrocarbon with a lactone; the reaction of a chlorinated hydrocanbon with chloromaleic acid or mercapto-maleic anhydride.

The mono-carboxylic and poly-carboxylic acid anhydrides are obtained by dehydrating the corresponding acids. Dehydration is readily accomplished by heating the acid to a temperature above about 70 C. preferably in the presence of a dehydration agent, e.g., acetic anhy- 8 dride. Cyclic anhydrides are usually obtained from poly-cariboxylic acids having the acid radicals separated by no more than three carbon atoms such as substituted succinic or glutaric acids, whereas linear polymeric anhydrides are obtained from poly-carboxylic acids having the acid radicals separated by four or more carbon atoms.

The acid halides of the mono-carboxylic and polycarboxylic acids can be prepared by the reaction of the acids or their anhydrides with a halogenation agent such as phosphorus tribromide, phosphorus pentachloride, or thionyl chloride. The esters of such acids can be prepared simply by the reaction of the acids or their anhydrides With an alcohol or a phenolic compound such as methanol, ethanol, octadecanol, cyclohexanol, phenol, naphthol, octylphenol, etc. The esterification is usually promoted by the use of an alkaline catalyst such as sodium hydroxide or sodium alkoxide or an acidic catalyst such as sulfuric acid. The nature of the alcoholic or phenolic portion of the ester radical appears to have little infiuence on the utility of such ester as reactant in the process described herein-above.

The nitrogen-containing reactants useful in the above process are the compounds, described previously in this specification, from which the nitrogen-containing group the acylated nitrogen compositions of this invention can be derived.

The above process is usually carried out by heating a mixture of the acid-producing compound and the nitrogen-containing reactant at a temperature above about C., preferably within the range from about C. to about 250 C. However, when an acid or anhydride is employed in reactions with an amino nitrogen-containingreactant, the process may be carried out at a lower temperature such as room temperature to obtain products having predominantly salt linkages or mixed saltamide linkages. Such products may be converted, if desired, by heating to above 80 C. to products having predominantly amide, imide, or amidine linkages. The use of a solvent such as benzene, toluene, naphtha, mineral oil, xylene, n-hexane, or the like is often desirable in the above process to facilitate the control of the reaction temperature.

Another method for preparing the acylated nitrogen compositions of this invention involves first reacting the nitrogen-containing reactant with an olefinic acid-producing compound to form a nitrogen containing intermediate and then incorporating a large hydrocarbon substituent (i.e., having at least about 50 aliphatic carbon atoms) into the intermediate by reacting the intermediate with a high molecular weight hydrocarbon reactant, such as an olefin, a chlorinated hydrocarbon, or a polar substituted hydrocarbon illustrated previously.

The olefinic acid-producing compound useful in the process may be an acid, anhydride, acid halide, or ester and it likewise may be an imide or amide derived from ammonia or a lower primary amine such as is described previously. The acid-producing compound may be that of maleic acid, itaconic acid, acrylic acid, aconitic acid, methacrylic acid, chloromaleic acid, alpha-chloroacrylic acid, alpha-butylacrylic acid, crotonic acid, citraconic acid, mesaconic acid, or a like acid preferably having less than about 8 carbon atoms and an olefinic linkage adjacent to the acid-producing radical.

Specific examples of such olefinic acid-producing compound include maleic acid, maleic anhydride, chloromaleic anhydride, maleamic acid, acrylic acid, acrylyl chloride, acrylyl bromide, methacrylic acid, alphapropylacrylyl chloride, crotonic acid, methyl acrylate, ethyl methacrylate, dimethyl maleate, diethyl itaconate, dibutyl maleate, maleimide, maleamide, N-methyl maleamide, dimethyl maleamide, N-butyl maleamide acid, N- propyl maleimide, methyl chlo-roacrylate, dimethyl citraconate, etc. The ester groups, imide groups, and amide groups of such olefinic acid-producing compounds include those discussed previously in connection with the high molecular weight acid-producing compounds useful in preparing the acylated nitrogen compositions of the invention.

The reaction of the nitrogen-containing reactant with an olefinic acid-producing compound may be carried out at a temperature from about 25 C. to 300 C. or any temperature below the decomposition point of the reaction mixture. The reaction is sirnilar to that which characterizes the formation of acylated nitrogen compositions described previously and results in a nitrogen-containing inter-mediate. The intermediate produced by such reaction is thus characterized by the presence therein of an amide, imide or amidine linkage or a mixture of such linkages. A convenient method of incorporating a high molecular weight hydrocarbon substituent into the nitrogen-containing intermediate involves reacting the intermediate with a high molecular weight reactant olefin, chlorinated hydrocarbon such as a chlorinated olefin polymer, or a polar substituted high molecular Weight hydrocarbon at a temperature above about 100 C., preferably below about 200 C. Such high molecular Weight reactant is as described previously in connection with the preparation of the high molecular weight succinic acidproducin-g compounds of this invention.

The relative proportions of the acid-producing compounds and the nitrogen-containing reactants to be used in the above process are such that at least about one-half of a stoichiometrically equivalent amount of the nitrogencontaining reactant is used for each equivalent of the acidproducing compound used. In this regard it will be noted that the equivalent weight of the nitrogen-containing reactant is based upon the number of the nitrogen-containing radicals defined by the structural configuration Similarly the equivalent weight of the acid-producing compound is based upon the number of the acid-producing radicals defined by the structural configuration Thus, ethylene diamine has two equivalents per mole; amino guanidine has four equivalents per mole; a succinic acid or ester has two equivalents per mole, etc. The upper limit of the useful amount of the nitrogen-containing reactant appears to be about two moles for each equivalent of the acid-producing compound used. Such amount is required, for instance, in the formation of products having predominantly amidine linkages. Beyond this limit, the excess amount of the nitrogen-containing reactant appears not to take part in the reaction and thus simply remains in the product apparently Without any adverse effects. On the other hand, the lower limit of about one-half equivalent of the nitrogen-containing reactant used for each equivalent of the acid-producing compound is based upon the stoichiome'try for the formation of products having predominantly imide linkages. In most instances, the preferred amount of the nitrogencontaining reactant is approximately one equivalent for each equivalent of the acid-producing compound used.

It should be noted that the reaction of a high molecular weight substituted succinic acid-producing compound (such as acid or anhyd-ride) with an alkylene polyamine (such as ethylene diamine or polyethylene polyamine) produces an acylated nitrogen composition which contains an amide conforming to the structural formula 0 R- CH%NR2 JI-IiO-NR2 where x is at least 1, R is a hydrocarbon group having at least about 50 aliphatic carbon atoms and at least about 25 aliphatic carbon atoms for each unit of x, and NR' is selected from the class consist-ing of (A) radicals derived 10 from an alyklene polyamine by the removal of a hydrogen atom from an amino group and (B) radicals derived from an alkylene polyamine by the removal of a hydrogen atom from an amino group and characterized by the presence, on the nitrogen atom of at least one additional amino group, of a complex substituent having the formula The value of x is at least one for each mole of the hydrocarbon substituent present in the amide molecule and it may be greater than one provided that it does not exceed one per each 50 aliphatic carbon atoms present in the hydrocarbon substituent. The radical R is the residue derived from an alkylene polyamine by the removal of one amino group; it may further contain a complex substituent (illustrated above) on the nitrogen atom of at least one additional amino group, or on the nitrogen atom of each of the other amino groups of the alkylene polyamine residue. In the latter case, the amide is illustrated by one present in the acylated nitrogen composition obtained by the reaction of one mole of an alkylene polyamine with as many equivalents of the substituted succinic acid or anhydride as there are amino groups in the polyamine.

The following examples illustrate the processes useful for preparing the acylated nitrogen compounds of this invention:

Example 1 A polyisobutenyl succinic anhydride is prepared by the reaction of a chlorinated polyisobutylene with maleic anhydride at 200 C. The polyisobutenyl radical has an average molecular weight of 850 and the resulting alkenyl succinic anhydride is found to have an acid number of 113 (corresponding to an equivalent weight of 500). To a mixture of 500 grams (1 equivalent) of this polyisobutenyl succinic anhydride and 160 grams of toluene there is added at room temperature 35 grams (1 equivalent) of diethylene triamine. The addition is made portionwise throughout a period of 15 minutes, and an initial exothermic reaction caused the temperature to rise to 50 C. The mixture then is heated and a water-toluene azeotrope distilled from the mixture. When no more water would distill the mixture is heated to C. at reduced pressure to remove the toluene. The residue is diluted with 350 grams of mineral oil and this solution is found to have a nitrogen content of 1.6%. The product is an oil solution of an acylated nitrogen composition containing an amide conforming to the structural formula where R is a polyisobutene radical, x has a value of one for each mole of the polyisobutene group, and NR is a radical derived from diethylene triamine by the removal of a hydrogen atom from an amino group and characterized by the presence on the nitrogen atom of at least one remaining amino group of a radical selected from the class consisting of Example 2 The procedure of Example 1 is repeated using 31 grams (1 equivalent) of ethylene diamine as the amine reactant. The nitrogen content of the resulting product is 1.4%.

Example 3 The procedure of Example 1 is repeated using 55.5 grams (1.5 equivalents) of an ethylene amine mixture having a composition corresponding to that of triethylene tetramine. The resulting product has a nitrogen content of 1.9%. The product is an oil solution of an acylated nitrogen composition containing an amide conforming to the structural formula shown in Example 1 except that R is derived from the ethylene amine mixture.

Example 4 The procedure of Example 1 is repeated using 55.0 grams (1.5 equivalents) of triethylene tetramine as the amine reactant. The resulting product has a nitrogen content of 2.9%. The product is an oil solution of an acylated nitrogen composition containing an amide conforming to the structural formula shown in Example 1 except that R is derived from triethylene tetramine.

Example 5 To a mixture of 140 grams of toluene and 400 grams (0.78 equivalent) of a polyisobutenyl succinic anhydride (having an acid number of 109 and prepared from maleic anhydride and the chlorinated polyisobutylene of Example 1) there is added at room temperature 63.6 grams (1.55 equivalents) of an ethylene amine mixture having an average composition corresponding to that of tetraethylene pentamine and available from Carbide and Carbon under the trade name Polyamine H. The mixture is heated to distill the water-toluene azeotrope and then to 150 C. at reduced pressure to remove the remaining toluene. The residual polyamide has a nitrogen content of 4.7%. The product is an oil solution of an acylated nitrogen composition containing an amide conforming to the structural formula shown in Example 1 except that R is derived from the ethylene amine mixture.

Example 6 The procedure of Example 1 is repeated using 46 grams 1.5 equivalents) of ethylene diamine as the amine reactant. The product which resulted has a nitrogen content of 1.5%. The product is an oil solution of an acylated nitrogen composition containing an amide conforming to the structural formula shown in Example 1 except that R is derived from ethylene diamine.

Example 7 A polyisobutenyl succinic anhydride having an acid number of 105 and an equivalent weight of 540 is prepared by the reaction of a chlorinated polyisobutylene (having an average molecular weight of 1,050 and a chlorine content of 4.3%) and maleic anhydride. To a mixture of 300 parts by weight of the polyisobutenyl succinic anhydride and 160 parts by weight of mineral oil there is added at 65 95 C. an equivalent amount (25 parts by weight) of Polyamine H (identified in Example 5). This mixture then is heated to 150 C. to distill all of the water formed in the reaction. Nitrogen is bubbled through the mixture at this temperature to insure removal of the last traces of water. The residue is diluted by 79 parts by weight of mineral oil and this oil solution found to have a nitrogen content of 1.6%. The product is an oil solution of an acylated nitrogen composition containing an amide conforming to the structural formula shown in Example 1 except that R is derived from the ethylene amine mixture.

Example 8 A mixture of 2,112 grams (3.9 equivalents) of the polyisobutenyl succinic anhydride of Example 7, 136

grams (3.9 equivalents) of diethylene triamine, and 1060 grams of mineral oil is heated at l50 C. for one hour. Nitrogen is bubbled through the mixture at this temperature for four more hours to aid in the removal of water. The residue is diluted with 420 grams of mineral oil and this oil solution is found to have a nitrogen content of 1.3%. The product is an oil solution of an acylated nitrogen composition containing an amide conforming to the structural formula showin in Example 1.

Example 9 To a solution of 1,000 grams (1.87 equivalents) of the polyisobuentyl succinic anhydride of Example 7, in 500 grams of mineral oil there is added at 85-95 C. 70 grams (1.87 equivalents) of tetraethylene pentamine. The mixture then is heated at -165 C. for four hours, blowing with nitrogen to aid in the removal of Water. The residue is diluted with 200 grams of mineral oil and the oil solution found to have a nitrogen content of 1.4%. The product is an oil solution of an acylated nitrogen composition containing an amide conforming to the structural formula shown in Example 1 except that R is derived from tetraethylene pentamine.

Example 10 A polypropenyl succinic anhydride is prepared by the reaction of a chlorinated polypropylene (having a molecular weight of about 900 and a chlorine content of 4%) and maleic anhydride at 200 C.. The product has an acid number of 75. To a mixture of 390 grams (0.52 equivalent) of this polypropenyl succinic anhydride, 500 grams of toluene, and grams of mineral oil there is added portionwise 22 grams (0.52 equivalent) of Polyamine H. The reaction mixture is heated at reflux temperature for three hours and water removed from an azeotrope with toluene. The toluene then is removed by heating to 150 C./2O millimeters. The residue was found to contain 1.3% of nitrogen. The product is an oil solution of an acylated nitrogen composition containing an amide conforming to the structural formula shown in Example 1 except that R is derived from the ethylene amine mixture.

Example 11 A substituted succinic anhydride is prepared by reacting maleic anhydride with a chlorinated copolymer of isobutylene and styrene. The copolymer consists of 94 parts by weight of isobutylene units and 6 parts by weight of styrene units, has an average molecular weight of 1,200, and is chlorinated to a chlorine content of 2.8% by weight. The resulting substituted succinic anhydride has an acid number of 40. To 710 grams (0.51 equivalent) of this substituted succinic anhydride and 500 grams of toluene there is added portion wise 22 grams (0.51 equivalent) of Polyamine H. The mixture is heated at reflux temperature for three hours to remove by azeot-ropic distillation all of the water formed in the reaction, and then at 150 C./20 millimeters to remove the toluene. The residue contains 1.1% by weight of nitrogen. The product is an oil solution of an acylated nitrogen composition containing an amide conforming to the structural formula shown in Example 1.

Example 12 A substituted succinic anhydride is prepared by reacting maleic anhydride with a chlorinated copolymer of isobutylene and isoprene. The copolymer consists of 99 parts by weight of isobutylene units and 1% by weight of isoprene units. The molecular weight of the copolymer is 28,000 and the chlorine content of the chlorinated copolymer is 1.95%. The resulting alkenyl succinic anhydride had an acid number of 54. To a mixture of 228 grams (0.22 equivalent) of an oil solution of this alkenyl succinic anhydride, 58 grams of additional mineral oil, 500 grams of toluene and 9.3 grams (0.22 equivalent) of Example 13 A polyisobutenyl succinic anhydride is prepared by the reaction of a chlorinated polyisobutylene with maleic anhydride. The chlorinated polyisobutylene has a chlorine content of 2% and an average molecular weight of 11,000. The polyisobutenyl succinic anhydride has an acid number of 48. A mixture of 410 grams (0.35 equivalent) of this anhydride, 15 grams (0.35 equivalent) of Polyamine H and 500 grams of toluene is heated at reflux temperature for four hours to remove water from an azeotrope with toluene. The toluene then is removed by heating to 150 C./20 millimeters. The nitrogen content of the residue is 1.3%. The product is an oil solution of an acylated nitrogen composition containing an amine conforming to the structural formula shown in Example 1.

Example 14 The procedure of Example is repeated except that 0.94 equivalent of Polyamine H is used instead of 1.55 equivalents. The nitrogen content of the product is 3%. The product is an oil solution of an acylated nitrogen composition containing an amide conforming to the structural formula shown in Example 1.

Example 15 A polyisobutenylsubstituted succinic acid is prepared by hydrolysis of the corresponding anhydride (prepared in turn by the condensation of a chlorinated polyisobutylene and maleic anhydride). To 1152 grams (1.5 equivalents) of a 70% mineral oil solution of this polyisobutylenyl succinic acid having an acid number of 62 there is added at room temperature 59.5 grams (1.5 equivalents) of Polyamine H. This mixture is heated at 150- 167 C. for 7 hours during which time a total of 19.5 grams of Water is distilled from the mixture. The residue is diluted with 174 grams of mineral oil and then filtered at 150 C. The filtrate has a nitrogen content of 1.6%. The product is an oil solution of an acylated nitrogen composition containing an amide conforming to the structural formula shown in Example 1.

Example 16 A mixture of 1056 grams (2.0 equivalents) of the polyisobutenyl succinic anhydride of the preceding example (in which the polyisobutenyl group has a molecular weight of 850), 89 grams (2.0 equivalents) of di-(l,2-propylene) triamine (having a nitrogen content of 31.3%), 370 grams of mineral oil and 100 grams of toluene is heated at reflux temperature (180-190= C.) for 5 hours. A total of 18 grams of water is collected from the water-toluene azeotrope. The residue is heated to 150 C./20 mm. to remove any last traces of water which might have remained. The nitrogen analysis of this residue is 1.9%. The product is an oil solution of an acylated nitrogen composition containing an amide conforming to the structural formula shown in Example 1 except that R is derived from di-( 1,2-propylene triamine.

Example 17 A polyisobutylene having an average molecular weight of 50,000 is chlorinated to a chlorine content of by Weight. This chlorinated polyisobutylene is reacted with maleic anhydride to produce the corresponding polyisobutenyl succinic anhydride having an acid number of 24. To 6,000 grams (2.55 equivalents) of this anhydride there is added portionwise at 70-105 C. 108

grams (2.55 equivalents) of :Polyamine H over a period of 45 minutes. The resulting mixture is heated for four hours at 1'601'80 C. While nitrogen is bubbled throughout to remove water. When all of the Water has been removed the product is (filtered and the filtrate found to have a nitrogen content of 0.6%. The product is an oil solution of an acylated nitrogen composition containing an amide conforming to the structural formula shown in Example 1 except that R is derived from the ethylene amine mixture.

Example 18 A mixture of 1 equivalent of a polyisobutene-substituted succinic anhydride having an acid number of 98 (prepared according to the procedure described in Example 1) and 1 equivalent of an acrolein-ammonia (molar ratio of 1: 1) interpolymer having a nitrogen content of 23% by Weight is diluted with 40% by its Weight of a mineral oil. The resulting mixture is heated to 155 C. and nitrogen is bubbled through the mixture at this temperature for 5 hours. The residue is found to have a nitrogen content of 1.35%.

Example 19 A cyanoethyl-substituted ethylene amine is prepared by mixing 21-2 grams of acrylonitrile with 216 grams of an ethylene amine mixture consisting of 75% by weight of triethylene tetramine and 25% by weight of diethylene triamine at room temperature and heating the mixture at l'l-0130 C. for 5 hours and then to C./mm. To a mixture of 111110 grams of the polyisobutene-substituted succinic anhydride of Example 1 and 825 grams of mineral oil there is added at 60 C. 143 grams dropwise of the above cyanoethyl-substituted ethylene amine (having a nitrogen content of 31.8%), The mixture is heated at C. C. for 5 hours while being purged with nitrogen. A total of 6 cc. of water is removed by distillation. The residue has a nitrogen content of 1.6 6%.

Example 20 To a mixture of 430 grams of the polyisobutenesubstituted succinic anhydride of Example 1 and 355 grams of mineral oil there is added at 60-80 C. 108 grams of N-aminopropyl morpholine throughout a period of 1 hour. The mixture is heated at 150-155 C. for 5 'hours until no more Water distills. The residue is found to have a nitrogen content of 2.3%.

Example 21 To a mixture of 1000 grams of the polyisobutenesubstituted succinic anhydride of Example 1 and 500 grams of mineral oil there is introduced at 150 1 60 C. beneath its surface a sufficient quantity of ammonia for formation of an imide within a period of 1 hour. The mixture is diluted with 169 grams of mineral oil, heated to 150 C. and filtered. The filtrate is found to have a nitrogen content of 0.77%.

Example 23 A mixture of 286 grams of polyisobutene-substituted succinic anhydride of Example 1, 96 grams of N, N-di- 'butyl ethylene-diamine and 252 grams of mineral oil is prepared at 60 C. and heated at 150-165 C. for 5 hours while being purged with nitrogen. The residue is found to have a nitrogen content of 2.24%.

15 Example 24 -A mixture of 417 grams of polyisobutene-substituted succinic anhydride of Example 1, 30 grams of N-(2- aminoethyl) trimethylene diamine and 293 grams of mineral oil is prepared at 6080 C. and then heated at 150155 C. -for hours while being purged with nitrogen. The residue is found to have a nitrogen content of 1.51%.

Example 25 A mixture of 430 grams of the polyisobutene-substituted succinic anhydride of Example 1, 64 grams of 1,l-(dimethylaminoethyl)-4-methyl-piperazine and 324 grams of mineral oil is prepared at 60 C. and then heated at 150-155 C. while being blown with nitrogen. The residue is found to have a nitrogen content of 1.81%.

Example 26 A mixture of 416 grams of polyisobutene-substituted succinic anhydride of Example 1, 124 grams of N-phenyl piperazine and 356 grams of mineral oil is prepared at 60 C. and then heated at l50-155 C. for 5 hours while being purged with nitrogen. No water is removed by such heating. The residue is found to have a nitrogen content of 2.07%.

Example 27 A mixture of 1110 grams of polyisobutene-substituted succinic anhydride of Example 1, 105 grams of anthranilic acid and 844 grams of mineral oil is heated at 100 C. for 2 hours. The mixture is cooled and is mixed with 72 grams of a mixture consisting of 75% by weight of triethylene tetramine and 25% by weight of diethylenetriamine at 6080 C. The resulting mixture is heated at 150-155 C. for 5 hours while being purged with nitrogen. The residue is found to have a nitrogen content of 1.72%.

Example 28 A diisobutenyl-substituted ethylene amine is prepared by reacting 590 grams of diisobutenyl chloride and 264 grams of a mixture consisting of 75 by weight of triethylene tetramine and 20% by weight of diethylene triamine in the presence of 264 grams of potassium hydroxide (85% purity) and 2200 grams of isopropyl alcohol at 85-90 C. A mixture of 528 grams of polyisobutene-substituted succinic anhydride of Example 1, 101 grams of the above diisobutenyl-substituted ethylene amine and 411 grams of mineral oil is heated at 150- 160 C. while being purged with nitrogen until no more water distills. The residue has a nitrogen content of 1.98%.

Example 29 A mixture of 45 grams of di-(polypropoxy)cocoamine having a molecular weight of 2265, 22 grams of polyisobutene-substituted succinic anhydride of Example 1 and 44 grams of mineral oil is heated at 150155 C. for 7 hours. The residue is found to have a nitrogen content of 0.25%.

Example 30 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, 159 grams of menthane diamine and 500 grams of mineral oil is prepared at 70100 C.- and heated at 150-190 C. while being blown with nitrogen until no water distills. The residue is diluted with 258 grams of mineral oil and the solution is found to have a nitrogen content of 1.32%.

Example 31 A polypropylene-substituted succinic anhydride having an acid number of 84 is prepared by the reaction of a chlorinated polypropylene having a chlorine content of 3% and molecular weight of 1200 with maleic anhydride. A mixture of 813 grams of the polypropylene-substi- 16 tuted succinic anhydride, 50 grams of a commercial ethylene amine mixture having an average composition corresponding to that of tetraethylene pentamine and 566 grams of mineral oil is heated at 150 C. for 5 hours. The residue is found to have a nitrogen content of 1.18%.

Example 32 A mixture of 206 grams of N,N'-disecondary-butyl p-phenylene diamine, 1000 grams of the polyisobutenesubstituted succinic anhydride of Example 1 and 500 grams of mineral oil is prepared at C. and heated at 150200 C. for 9.5 hours. The mixture is diluted with 290 grams of mineral oil, heated to 160 C. and filtered. The filtrate is found to have a nitrogen content of 1.29%.

Example 33 To 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1 and 500 grams of mineral oil there is added 17.6 grams of hydrazine at 70-80 C. The reaction is exothermic. The mixture is heated at 140150 C. for 1 hour whereupon 9 grams of water is collected as the distillate. To the residue there is then added 40 grams of an ethylene amine mixture having an average composition corresponding to that of tetraethylene pentamine at 70-80 C. The mixture i then heated at 150160 C. while being purged with nitrogen until no more water is removed by distillation. The residue is diluted with 200 grams of mineral oil, heated to 160 C. and filtered. The filtrate has a nitrogen content of 1.16%.

Example 34 T o a solution of 1000 grams of the polyisobutene-substituted snccinic anhydride of Example 1 in 500 grams of mineral oil there is added 28 grams of 1,1-dimethyl hydrazine at 5060 C. The mixture is heated at 60- C. for 3 hours and then mixed with 40 grams of an ethylene amine mixture having an average composition corresponding to that of tetraethylene pentamine at 85- 95C. The mixture is then heated at 150-185 C. for 6 hours whereupon 14 grams of water is collected as the distillate. The residue is diluted with 197 grams of mineral oil, heated to 160 C. and filtered. The filtrate has a nitrogen content of 1.53%.

Example 35 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, 333 grams of 1,2-di(3-aminopropoxy) ethane and 500 grams of mineral oil is heated at 170 C. for 5 hours whereupon 18 grams of Water is collected as the distillate. The residue is diluted with 380 grams of mineral oil, heated to 160 C. and filtered. The filtrate has a nitrogen content of 2.3%.

Example 36 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, 418 grams of di- (3-aminopropoxy ethyl) ether and 500 grams of mineral oil is heated at 170 C. for 4 hours. A total of 17 grams of water is collected as the distillate. The residue is diluted with 433 grams of mineral oil heated to 160 C. and filtered. The filtrate has the nitrogen content of 2.18%.

Example 37 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1 and 361 grams of a technical tertiary-alkyl primary amine wherein the tertiary-alkyl radical contains 12-14 carbon atoms and 500 grams of mineral oil is heated at 250 C. for 13 hours while being purged with nitrogen. The residue is then heated to 150 C./1 mm., diluted with 337 grams of mineral oil, heated to C. and filtered. The filtrate has a nitrogen content of 0.87%.

1 7 Example 38 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, 254 grams of aminoguanidine bicarbonate and 500 grams of mineral oil is prepared at 80 C. and heated at 130-165 C. for hours. The residue is mixed with 223 grams of mineral oil, heated to 150 C., and filtered. The filtrate has the nitrogen content of 3.38%.

Example 39 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, 178 grams of Z-amino-pyridine and 500 grams of mineral oil is heated at 140175 C. for 10 hours while being purged with nitrogen. A total of 16 grams of water is collected as the distillate. The residue is diluted with 273 grams of mineral oil and filtered. The filtrate ha a nitrogen content of 2.55%.

Example 40 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, 103 grams of 2,6-diamino-pyridine and 500 grams of mineral oil is heated at 140-180 C. for 11 hours while being purged with nitrogen. A total of 16 grams of Water is collected as the distillate. The residue is diluted with 223 grams of mineral oil, heated to 150 C. and filtered. The filtrate has a nitrogen content of 2.15%.

Example 41 A mixture of 1000 grams of polyisobutene-substituted succinic anhydride of Example 1, 159 grams of cyanoguanidine and 233 grams of toluene is heated at the reflux temperature of 14 hours while 7.15 grams of water is removed by azeotropic distillation. The mixture is diluted With 740 grams of mineral oil and toluene is then removed by heating the mixture to 150 C. The residue is filtered and the filtrate has the nitrogen content of 4.74%.

Example 42 A mixture of 1632 grams of polyisobutene-substituted succinic anhydride of Example 1, 207 grams of a condensation product of acrolein with ammonia (molar ratio of 1:1) having a nitrogen content of 20%, 604 grams of mineral oil and 1750 grams of toluene is heated at the reflux temperature for 3 hours. A total of 31 grams of water is removed as the distillate. Toluene is then removed by heating the mixture to 150 C./ 20 mm. The residue is found to have a nitrogen content of 1.89%.

Example 43 I A nitrogen-containing compound is prepared by mixing 100 grams of cyanoguanidine with 500 grams of ethylene amine mixture having an average composition corresponding to that of tetraethylene pentamine and heating the mixture at 70-80 C. for 3 hours to obtain a homogeneous mass and filtering the mass. A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, 96 grams of the above filtrate and 164 grams of toluene is heated at the reflux temperature for 10 hours. The toluene is then removed by heating the mixture to 150 C./2O mm. The residue is diluted with 400 grams of mineral oil and filtered. The filtrate has a nitrogen content of 3.43%.

Example 44 To a mixture of 544 .grams of the polyisobutene-substituted succinic anhydride of Example 1, 283 grams of mineral oil and 281 grams of toluene there is added 30 grams of urea at 45 C. The resulting mixture is heated at 130-135 C. for 11 hours whereupon 2.5 cc. of Water is removed as the distillate. The residue is then heated to 140 C./20 mm. and filtered. The filtrate has a nitrogen content of 1%.

18 Example 45 A mixture of 1088 grams of the polyisobutene-substituted succinic anhydride of Example 1, 106 grams of dipropylene triamine, 500 grams of toluene is heated at the reflux temperature for 4 hours until no more Water distills. The residue is then heated to C./20 mm. and diluted with 392 grams of mineral oil. The oil solution is found to have a nitrogen content of 1.74%.

Example 46 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, 174 grams of phenylbiguanide and 270 grams of toluene is heated at the reflux temperature for 6.5 hours whereupon 25 grams of water is removed by distillation. The residue is diluted With 500 grams of mineral oil and heated to C./2O mm. to distill ofi toluene. The residue is diluted further with 265 grams of mineral oil, heated to 150 C. and filtered. The filtrate has a nitrogen content of 3.4%.

Example 47 A mixture of 920 grams of the polyisobutene-substituted succinic anhydride of Example 1, and 249 grams of bis-(dimethylaminopropyl) amine is heated at reflux temperature until no more water distills. The residue has a nitrogen content of 4%.

Example 48 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, 363 grams of aminopropyl octadecylamine and 1314 grams of mineral oil is heated at 200 C. for 24 hours. The residue is filtered. The filtrate has a nitrogen content of 1.02%.

Example 49 A mixture of 1000 grams of the polyisobutene-substituted succinic anhydride of Example 1, and 258 grams of di-n-butylamine is heated at C. for 12 hours and then to 200 C./ 25 mm. The residue is diluted with 1157 grams of mineral oil and filtered. The filtrate has a nitrogen content of 0.8%.

Example 50 A mixture of 297 grams of the polyisobutene-substituted succinic anhydride of Example 1, 25 grams of melamine and 200 grams of mineral oil is heated at -260 C. for 9 hours and then at 290295 C. for 7 more hours. The residue is mixed with 50 grams of water, heated at reflux for 7 hours, dried and filtered. The filtrate has a nitrogen content of 2%.

Example 51 A mixture of 100 grams of the polyisobutene-substituted anhydride of Example 1 and 67 grams of mineral oil is heated to 50 C. To this mixture there is added 59 grams of an 85% aqueous solution of hydrazine hydrate. The mixture is heated at 100110 C. for 1.25 hours, diluted with toluene, and heated at 107 C. until no more water distills. Toluene is removed by distillation. The residue has a nitrogen content of 0.8%.

Example 52 A mixture of 1.0 equivalent of a mono-carboxylic acid (prepared by chlorinating a polyisobutene having a molecular weight of 750 to a product having a chlorine content of 3.6% by weight, converting the product to the corresponding nitrile by reaction with an equivalent amount of potassium cyanide in the presence of a catalytic amount of cuprous cyanide and hydrolyzing the resulting nitrile by treatment with 50% excess of a dilute aqueous sulfuric acid at the reflux temperautre) and 0.5 equivalent of ethylene diamine is mixed with twice its volume of xylene. The resulting mixture is heated at the reflux temperature until no more water is removed by distillation. The mixture is heated further and the xylene is 19 removed by distillation under reduced pressure. residue is the acylated nitrogen compound.

Example 53 A methyl ester of a high molecular weight mono-carboxylic acid is prepared by heating an equi-molar mixture of a chlorinated polyisobutene having a molecular weight of 1000 and a chlorine content of 4.7% by weight and methyl methacrylate at l40220 C. The resulting ester is then heated with a stoichiometrically equivalent amount of triethylene tetramine at 100200 C. to produce an acylated nitrogen compound of this invention.

Example 54 A dimethyl wax-substituted malonate is prepared by reacting dimethyl malonate with sodium ethoxide to form a sodium derivative of the ester, heating the sodium derivative with a brominated wax having 75 carbon atoms and 1 bromine atom per molecule. A mixture of 1.0 equivalent of the ester of 1.0 equivalent of N,N-dibuty1 thiourea is dissolved in five times its volume of xylene. The resulting mixture is heated at the reflux temperature until no more water is removed by azeotropic distillation. The mixture is heated further and the xylene is removed by distillation. The residue is the acylated nitrogen compound.

The

Example 55 A high molecular weight mono-carboxylic acid is prepared by telomerizing ethylene with carbon tetrachloride to a telomer having an average of 35 ethylene radicals per molecule and hydrolyzing the telomer to the corresponding acid in accordance with the procedure described in British Patent No. 581,899. A mixture of 1.5 equivalent of the acid and 0.75 equivalent of amino-propy-l octylamine is mixed with twice its volume of a mineral oil and twice its volume of xylene. The resulting mixture is heated at the reflux temperature until no more water is removed by azeotropic distillation. Xylene is then removed by distillation under reduced pressure and the residue is filtered.

Example 56 A mixture of 2000 grams of mineral oil, 3 equivalents of trimethylene diamine and 3 equivalents of a high molecular weight tricarboxylic acid prepared by the reaction of a brominated poly (l-hexene) having a molecular weight of 2000 and a bromine content of 4% by weight of 2-pentene-1,3,5-tricarboxylic acid (prepared by dehydration of citric acid) is heated at 150 C. for 20 hours. The residue is filtered to give a homogeneous mineral oil solution of the acylated nitrogen product.

Example 57 An equi-molar mixture of 2-aminoethyl morpholine and a mono-carboxylic acid (prepared by the reaction of ketene with a brominated poly(1-octene) having a molecular weight of 1500 and one atom of bromine per molecule) is diluted with three times its volume of xylene. The resulting mixture is heated at the reflux temperature until no more water is removed by distillation. The residue is an xylene solution of the :acylated nitrogen compound.

Example 58 A mixture of 1 equivalent of methane diamine and 1 equivalent of a high molecular glutaric acid-ester (prepared by the reaction of silver with an equi-molar mixture of beta-iodopropanoic acid and alpha-iodo derivative of the methyl ester of the mono-carboxylic acid of the preceding example) is diluted with an equal weight of a mineral oil and the resulting solution is heated at 180 C. until no more water distills. The residue is then filtered.

Example 59 An equi-molar mixture of a technical ethylene amine mixture having an average composition corresponding to A high molecular weight dicarboxylic acid is prepared by reacting two moles of the Omega-brorno derivative of the hexapentacontanoic acid of the preceding example with one mole of zinc. The dicarboxylic acid is then treated with 2 equivalents of ethylene diamine to produce a diamide.

Example 61 A mixture of 1 equivalent of 1-aminoethyl-2-octadecylimidazoline with 1 equivalent of the high molecular weight monocarboxylic acid of Example is mixed with twice its volume of diphenyl oxide. The resulting mixture is heated at the reflux temperature until no more water distills. The residue is then filtered.

Example 62 A product is obtained by the procedure described in the preceding example except that N,N'-di-n-butyl-p-phenylenediamine (1 equivalent) is used in lieu of the imidazoline used.

Example 63 To a solution of 1 equivalent of di-methyl ester of a polyethylene (molecular weight of 1500)-substituted malonic acid in 5000 grams of xylene, there is added 1 mole of melamine at C. The resulting mixture is heated at the reflux temperature for 25 hours. The residue is mixed with 2000 grams of mineral oil and xylene is removed by heating the oil solution to 180 C./2 mm.

Example 64 A product is obtained by the procedure of Example 1, except that pyrrolidine (1 equivalent) is used in lieu of the diethylene triamine used.

Example 65 A product is obtained by the procedure of Example 1, except that hexahydro-1,3,5-triazine (1 equivalent) is used in lieu of the diethylene triamine used.

Example 66 A product is obtained by the procedure of Example 1, except that 1,3,4-dithiazolidine (1 equivalent) is used in lieu of the ethylene diamine used.

Example 67 A product is obtained by the procedure of Example 1, except that hexamethylene tetramine (2 equivalents) is used in lieu of the ethylene diamine used.

Example 68 A product is obtained by the procedure of Example 1, except that tripentylene tetramine (3 equivalents) is used in lieu of the ethylene diamine used.

Example 69 An equi-molar mixture of the polyisobutene-substituted succinic anhydride of Example 1 and N-octyl thiourea is diluted with an equal volume of xylene. The resulting mixture is heated at the reflux temperature for 30 hours. The residue is a xylene solution of the product.

Example 70 A product is obtained by the procedure of Example 69 except that oleylamide is used in lieu of the thiourea used.

21 Example 71 A product is obtained by the procedure of Example 69 except that 1,3-diphenyl guanidine is used in lieu of the thiourea used.

Example 72 A product is obtained by the procedure of Example 69 except that octadecamidine is used in lieu of the thiourea used.

Example 73 A product is obtained by the procedure of Example 69 except that guanylurea is used in lieu of the thiourea used.

Example 74 To a mixture of 396 grams of the polyisobutene-substituted succinic anhydride of Example 1 and 282 grams of mineral oil there was added 34 grams of N-methyltrimethylene diamine at 60 C. Within a period of one hour. The mixture was blown with nitrogen at 150- 155 C. for hours. The residue was found to have a nitrogen content of 1.41%.

Example 75 A mixture of 308 grams of mineral oil, 400 grams of the polyisobutene-substituted succinic anhydride of Example 1, and 70 grams of N-(2-ethylhexyl)-trimethylene diamine was prepared at 60 C. The mixture was heated to 250 C. and was then blown with nitrogen at 150- 155 C. for 5 hours. The residue had a nitrogen content of 1.4%.

Example 76 A mixture of 386 grams of mineral oil, 528 grams of the polyisobutene-suostituted succinic anhydride of Example 1, and 59 grams of N-(2-hydroxyethyl)-trimethylenediamine was prepared at 60 C. The mixture was blown with nitrogen at 150-155 C. for 5 hours. The residue had a nitrogen content of 1.56%.

Example 77 A mixture of 185 grams of mineral oil, 330 grams of the polyisobutene-substituted succinic anhydride of Example 1, and 88.5 grams of 1,4-bis(2-hydroxypropyl)-2- methyl piperazine was prepared at 60 C. The mixture was heated at 180-276 C./40 mm. for 14.5 hours. The residue had a nitrogen content of 1.12%.

Example 78 To a mixture of 314 grams of mineral oil and 430 grams of of the polyisobutene-substituted succinic anhydride of Example 1 there was added at 60 C., 49 grams of 1-(2-hydroxyethyl)piperazine. The mixture was heated to 150 C. and blown with nitrogen at this temperature for 5 hours. The residue had a nitrogen content of 1.38%.

Example 79 A mixture of 382 grams of mineral oil, 528 grams of polyisobutene-substituted succinic anhydride of Example 1, and 53 grams of 1-methyl-4-(3-aminopropyl)piperazine was prepared at 60 C., heated to 150 C., and blown with nitrogen at 150155 C. for 5 hours. The residue had a nitrogen content of 1.57%.

Example 80 To a mixture of 800 grams of the polyisobutene-substituted succinic anhydride of Example 1 and 175 grams of toluene there was added 77 grams of a commercial mixture of alkylene amines and hydroxy alkyl-substituted alkylene amines consisting of approximately 2% (by weight) of diethylene triamine, 36% of 1-(2-aminoethyl)piperazine, 11% of 1-(Z-hydroxyethyl)piperazine, 11% of NlZ-hydroxyethyl)ethylenediamine, and 40% of higher homologues obtained as a result of condensation of the above-indicated amine components. The result- 22 ing mixture Was heated at the reflux temperature for 16.5 hours whereupon 12 cc. of water was collected as the distillate. The residue was then heated to 160 C./25 mm. and diluted with 570 grams of mineral oil. The final product was found to have a nitrogen content of 1.57%.

Example 81 A product is obtained by the procedure of Example 69 except that an equimolar mixture of ammonia and bis(2-hydroxyethyl)amine is used in lieu of the thiourea used.

Example 82 A product is obtained by the procedure of Example 69 except that an equimolar mixture of benzidine is is used in lieu of the thiourea used.

Example 83 An alkenyl succinic anhydride in which the alkenyl group has less than 50 carbon atoms is prepared from a polyisobutylene having an average molecular weight of 375. This polymer is chlorinated to a chlorine content of 9.7% and then reacted with maleic anhydride. The resulting polyisobutenyl succinic anhydride has an acid number of 190 and an equivalent weight of 300. The procedure of Example 1 is followed using 1.0 equivalent of this polyisobutenyl succinic anhydride and 1.0 equivalent of Polyamine H. The resulting product then is diluted with mineral oil to a 58% solution therein; the nitrogen content is 3.2%

Example 84 Another alkenyl succinic anhydride in which the alkenyl group has less than 50 carbons is prepared by alkylation of maleic anhydride with tetra-propylene. Equivalent amounts of this tetrapropenyl succinic anhydride and triethylene tetramine in toluene are heated at reflux temperature until substantially all of the water is removed. The toluene then is removed by heating at 155 C. under reduced pressure and the residue is dissolved in mineral oil to a 60% solution. This oil solution is found to have a nitrogen content of 4.8%.

Example 85 A polyisobutene having an average molecular weight of 520 corresponding to 37 carbon atoms) is chlorinated to a chlorine content of 6.25% and then is made to react with an equivalent amount of maleic anhydride to yield a polyisobutene-substituted succinic anhydride having a saponification of 152. To 552 grams (1.5 equivalents) of this anhydride dissolved in 276 grams of mineral oil there is added at 60 C. 63 grams (1.5 equivalents) of Polyamine H portionwise over a period of 1 hour. The resulting mixture is heated for 6 hours at 150 C. and then blown with nitrogen at this temperature for 1 hour. The residue is diluted with grams of mineral oil and the final oil solution is found to have a nitrogen content of 2.1%.

Example 86 A mixture of 1 equivalent of maleimide (i.e.,

and 1 equivalent of a chlorinated polyisobutene having a chlorine content of 4.34% and a molecular weight of 350 is heated to C. in 2 hours and then blown with nitrogen at 150-204 C., cooled, diluted with benzene, mixed with a filter aid and filtered. The filtrate is heated to C./30 mm. to remove volatile materials. The residue is a polyisobutene-substituted succinimide having a nitrogen content of 1.44%. A mixture of this substituted succinimide (58.3 grams, 0.06 equivalent of nitrogen), tetraethylene pentamine (9.9 grams, 0.24 equivalent of nitrogen), and mineral oil (44.8 grams) is heated at 150-455 C. for 2.75 hours, cooled to room tem- 23 perature, diluted with benzene (500 grams), mixed with a filter aid and filtered. The filtrate is heated at 135 C./40 mm. to remove volatile materials. The residue is an oil solution of the desired acylated tetraethylene pentamine and has a nitrogen content of 2.94%.

Example 87 A mixture of 1 equivalent of N-butyl maleimide and 1 equivalent of a chlorinated polyisobutene having a chlorine content of 4.33% and a molecular wieght of 850 is heated at 100 C".210 C. in nitrogen atmosphere and then heated at l03114 C./12l mm. The reaction mixture is then filtered and the filtrate is an N-butyl polyisobutene substituted succinimide having a nitrogen content of 1.23%. A mixture of this substituted N-butyl succinimide (177 grams, 0.156 equivalent of nitrogen) and tetraethylene pentamine (12.8 grams, 0.311 equivalent of nitrogen) is diluted with mineral oil (86 grams) and heated at 150158 C. in nitrogen atmosphere. The reaction mixture is diluted with mineral oil (41 grams) and filtered. The filtrate is blown with nitrogen at 190204 C. for 5 hours, heated at 140/1 mm. and again blown with nitrogen at 24025S C. for 5.9 hours. The mixture is filtered. The filtrate is an oil solution of an acylated polyamine and has a nitrogen content of 1.13

Example 88 A mixture of 1 equivalent of maleic anhydride and 2 equivalents of tetraethylene pentamine is heated at a temperature of 100-180 C. to form an intermediate product. The intermediate product is then mixed with 1 equivalent of a chlorinated polyisobutene having a chlorine content of 4% and a molecular weight of 1500 at 150-2l0 C. The product is diluted with equal Weight of mineral oil and filtered. The filtrate is an oil solution of the acylated polyamine.

Example 89 The procedure of Example 88 is repeated except the chlorinated polyisobutene is replaced on a weight basis with a polyisobutene having a molecular weight of 2000.

Example 90 A polyisobutene having a molecular weight of 1000 (1000 grams) and maleic anhydride (100 grams), is heated at 150220 C. to form a polyisobutene-substituted maleic anhydride. The anhydride is then mixed with tetraethylene pentamine (1.5 equivalents per equivalent of anhydride) and the mixture is heated at 18020'0 C. to form an acylated polyamine.

Example 91 An acid producing compound is prepared by heating chloromaleic anhydride (1 equivalent) and 1 equivalent of a chlorinated polyisobutene having a chlorine content of 4% and a molecular weight of 2500 at 150200 C. The product of the reaction is then mixed with tetraethylene pentamine (2.5 equivalents) at 50 C. and the mixture is heated at 180-210 C. to form an acylated polyamine.

Example 92 A substituted monocarboxylic acid producing compound is obtained by reacting acrylic acid (1 equivalent) with a chlorinated polyisobutene (1 equivalent) having a chlorine content of 4.5% and a. molecular weight of 850 at 150200 C. The product of the reaction is then mixed with 1.25 equivalents of pentaethylene hexamine at 5075 C. and the resulting mixture is heated at 180-200 C. to form an acylated polyamine.

Example 93 The procedure of Example 92 is repeated except that the acrylic acid is replaced on a chemically equivalent basis with alpha-chloroacrylic acid and the pentaethylene hexamine is replaced on a nitrogen basis with ethylene diamine.

Example 94 The procedure of Example 91 is repeated except that the acid-producing compound used is one which is obtained by the reaction (Haloform reaction) of methyl heptapentacontanyl ketone with iodine, sodium hydroxide, and acidification of the haloform product.

Example 95 The procedure of Example 91 is repeated except that the acid-producing compound used is one which is obtained by the reaction of equivalent amounts of the chlorinated polyisobutene with methyl ester of N-butyl maleamic acid.

Example 96 The polyisobutene-substituted succinimide is obtained by reacting the polyisobutene-substituted succinic anhydride of Example 1 with ammonia (0.5 equivalent per equivalent of the anhydride). A mixture of the succinimide (1 equivalent of nitrogen) and tetraethylene penta mine (1 equivalent of nitrogen) is diluted with an equal weight of mineral oil and heated at 180 -250 C. to effect trans-amidation. The product is an acylated tetraethylene pentamine.

Example 97 The procedure of Example 96 is repeated except that the succinimide is N-methyl polyisobutene-substituted succinimide obtained by reacting the corresponding polyisobutene-substituted succinic anhydride with methylamine (0.5 equivalent per equivalent of the anhydride).

Example 98 The procedure of Example 96 is repeated except that the succinimide is N phenyl polyisobutene-substituted succinimide obtained by reacting the corresponding polyisobutene-substituted succinic anhydride with aniline (0.5 equivalent per equivalent of the anhydride).

Example 99 A polyisobutene-substituted succinamide is obtained by reacting 1 equivalent of the polyisobutene-substituted succinic anhydride of Example 1 with 1 equivalent of dimethylamine. The succinamide so obtained is then reacted with 2 equivalents of pentaethylene hexamine at 160-210 C. to effect trans-amidation and form an acylated polyamine.

Example 100 The procedure of Example 88 is repeated except that maleic anhydride used is replaced with itaconic acid on a stoichiometrically equivalent basis.

As indicated previously the acylated nitrogen-containing composition is usually present in lubricating oils in amounts ranging from about 0.1% to about 10% by weight. The optimum amounts for a particular application depend to a large measure upon the type of surface to which the lubricating composition is to be subjected. Thus, for example, lubricating compositions for use in gasoline internal combustion engines may contain from about 0.5 to about 5% of an acylated nitrogen-containing composition, whereas lubricating compositions for use in gears and diesel engines may contain as much as 10% or even more of the additive.

This invention contemplates also the presence of other additives in the lubricating compositions. Such additives include, for example, detergents of the ash-containing type, viscosity index improving agents, pour point depressing agents, anti-foam agents, extreme pressure agents, rust-inhibiting agents, and oxidation and corrosion inhibiting agents.

The ash-containing detergents are exemplified by oilsoluble neutral and basic salts of alkali or alkaline earth metals with sulf-onic acids, carboxylic acids, or organic phosphorus acids characterized by at least one direct carbon-to-phosphorus linkage such as those prepared by the treatment of an olefin polymer (e.g., polyisobutene having a molecular weight of 1000) with a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride. The most commonly used salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, strontium, and barium.

The term basic salt is used to designate the metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical. The commonly employed methods for preparing the basic salts involves heating a mineral oil solution of an acid with a stoichiometric excess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 50 C. and filtering the resulting mass. The use of a promoter in the neutralization step to aid the incorporation of a large excess of metal likewise is known. Examples of compounds useful as the promoter include phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation products of formaldehyde with a phenolic substance; alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; amines such as aniline, phenylenediamine, phenothiazine, phenylbeta-naphthylamine, and dodecylamine. A particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent, a phenolic promoter compound, and a small amount of water and carbonating the mixture at an elevated temperature such as 60-200 C.

Extreme pressure agents and corrosion-inhibiting and oxidation-inhibiting agents are exemplified by chlorinated aliphatic hydrocarbons such as chlorinated wax; organic sulfides and polysulfides such as benzyl disulfide, bis- (chlorobenzyDdisulfide, dibutyl tetrasulfide, sulfurized sperm oil, sulfurized methyl ester of oleic acid, sulfurized alkyphenol, sulfurized dipentene, and sulfurized terpene; phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate; phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite, dipentyl phenyl phoshite, tridecyl phosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite, polypropylene (molecular weight 500)-substituted phenyl phosphite, diisobutylsubstituted phenyl phosphite; metal thiocarbamates, such as Zinc dioctyl-dithiocarbamate, and barium heptylphenyl dithiocarbamate: Group 11 metal phosphorodithioates such as zinc dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, barium di(heptylphenyl) phosphorodithioate, cadmium dinonylphosphorodithioate, and zinc salt of a phosphorodithioic acid produced by the reaction of phosphorus pentasulfide with an equimolar mixture of isopropyl alcohol and n-hexyl alcohol.

The lubricating compositions may also contain metal detergent additives in amounts usually within the range of about 0.1% to about 20% by weight. In some applications such as in lubricating marine diesel engines the lubricating compositions may contain as much as of a metal detergent additive. They may also contain extreme pressure addition agents, viscosity index improving agents, and pour point depressing agents, each in amounts within the range of from about 0.1% to about 10%.

The following examples are illustrative of the lubricating compositions of this invention: (all percentages are by weight) 26% Example A SAE 20 mineral lubricating oil containing 0.5% of the product of Example 1.

Example B SAE 30 mineral lubricating oil containing 0.75% of the product of Example 2 and 0.1% of phosphorus as the barium salt of di-n-nonylphosphorodithioic acid.

Example C SAE 10W-30 mineral lubricating oil containing 0.4% of the product of Example 7.

Example D SAE mineral lubricating oil containing 0.1% of the product of Example 7 and 0.15% of the zinc salt of an equimolar mixture of di-cylohexylphosphorodithioic acid and di-isobutyl phosphorodithioc acid.

Example E SAE 30 mineral lubricating oil containing 2% of the product of Example 3.

Example F SAE 20W-30 mineral lubricating oil containing 5% of the product of Example 14.

Example G SAE 10W-30 mineral lubricating oil containing 1.5% of the product of Example 25 and 0.05% of phosphorous as the zinc salt of a phosphorodithioic acid prepared by the reaction of phosphorus pentasulfide with a mixture of 60% (mole) of p-butylphenol and 40% (mole) of npentyl alcohol.

Example H SAE 50 mineral lubricating oil containing 3% of the product of Example 36 and 0.1% of phosphorus as the calcium salt of di-hexylphosphorodithioate.

Example I SAE 10W-30 mineral lubricating oil containing 2% of the product of Example 48, 0.06% of phosphorus as zinc di-n-octyl-phosphorodithioate, and 1% of sulfate ash as barium mahogany sulfonate.

Example I SAE 10W-30 mineral lubricating oil containing 6% of the product of Example 60, 0.075% of phosphorus as zinc di-n-octylphosphorodithioate, and 5% of the barium salt of an acidic composition prepared by the reaction of 1000 parts of a polyisobutene having a molecular weight of 60,000 with parts of phosphorus pentasulfide at 200 C. and hydrolyzing the product with steam at C.

Example L SAE 10 mineral lubricating oil containing 2% of the product of Example 74, 0.075% of phosphorus as the adduct of zinc di-cyclohexylphosp-horodithioate treated with 0.3 mole of ethylene oxide, 2% of sulfurized sperm oil having a sulfur content of 10%, 3.5% of a poly-(alkyl methacrylate) viscosity index improver, 0.02% of a poly- (alkyl methacrylate) pour point depressant, 0.003% of a poly-(alkyl siloxane) anti-foam agent.

27 Example M SAE 10 mineral lubricating oil containing 1.5% of the product of Example 51, 0.075 of phosphorus as the ad duct obtained by heating zinc di-nonylphosphordithioate with 0.25 mole of 1,2-hexene oxide at 120 C., a sulfurized methyl ester of tall oil acid having .a sulfur content of 15%, 6% of a polybutene vicosity index improver, 0.005% of a poly-(alkyl methacrylate) anti-foam agent, and 0.5% of lard oil.

Example N SAE 20 mineral lubricating oil containing 1.5% of the product of Example 13, 0.5% of di-dodecyl phosphite, 2% of the sulfurized sperm oil having a sulfur content of 9%, a basic calcium detergent prepared by carbonating a mixture comprising mineral oil, calcium mahogany sulfonate and 6 moles of calcium hydroxide in the presence of an equi-molar mixture 10% of the mixture) of methyl alcohol and n-butyl alcohol as the promoter at the reflux temperature.

Example SAE 10 mineral lubricating oil containing 2% of the product of Example 7, 0.07% of phosphorus as zinc diocytlphosphorodithioate, 2% of a barium detergent prepared by neutralizing with barium hydroxide the hydrolyzed reaction product of a polypropylene (molecular weight 2000) with 1 mole of phosphorus pentasulfide and 1 mole of sulfur, 3% of a barium sulfonate detergent prepared by carbonating a mineral oil solution of mahogany acid, and a 500% stoichiometrically excess amount of barium hydroxide in the presence of phenol as the promoter at 180 C., 3% of a supplemental ashless detergent prepared by copolymerizing a mixture of 95% (weight) of decyl-methacrylate and (weight) of diethylamino-ethylacrylate.

Example P SAE 80 mineral lubricating oil containing 2% of the product of Example 7, 0.1% of phosphorus as zinc di-nhexylphosphorodithioate, of a chlorinated parafiin wax having a chlorine content of 40%, 2% of di-butyl tetrasulfide, 2% of sulfurized dipentene, 0.2% of oleyl amide, 0.03% of an anti-foam agent, 0.02% of a pour point depressant, and 3% of a viscosity index improver.

Example Q SAE 10 mineral lubricating oil containing 3% of the product of Example 16, 0.075% of phosphorus as the zinc salt of a phosphorodithioic acid prepared by the reaction of phosphorus pentasulfide with an equimolar mixture of n-butyl alcohol and dodecyl alcohol, 3% of a barium detergent prepared by carbonating a mineral oil solution containing 1 mole of sperm oil, 0.6 mole of octylphenol, 2 moles of barium oxide, and a small amount of water at 150 C.

Example R SAE 20 mineral lubricating oil containing 2% of the product of Example 17 and 0.07% of phosphorus as zinc di-n-octyl-phosphorodithioate.

Example S SAE 30 mineral lubricating oil containing 3% of the product of Example 48 and 0.1% of phosphorus as zinc di-(isobutyl-phenyl)-phosphorodithioate.

Example T SAE 50 mineral lubricating oil containing 2% of the product of Example 39.

Example U SAE 90 mineral lubricating oil containing 3% of the product of Example 20 and 0.2% of phosphorus as the reaction product of 4 moles of turpentine with 1 mole of phosphorus pentasulfide.

The above lubricants are merely illustrative and the scope of invention includes the use of all of the additives previously illustrated as well as others within the broad concept of this invention described herein.

The utility of the dispersant additives of this invention is shown by the results of an evaluation of the crankcase lubricants used in taxicabs which had been operated for over 50,000 miles each. In this test ten 6-cylinder 1958 Chevrolet cars (with no oil filters) were operated as a fleet of taxicabs. In each case the crankcase lubricant was a solvent refined Mid-Continent petroleum oil having a viscosity of 185 SUS/ F. and a viscosity index of 112, and containing 5.9% by volume of a poly-alkylrnethacrylate viscosity index improver and 0.59% by volume of a zinc dialky'l phosphorodithioate (the alkyl groups being isobutyl and a mixture of primary amyl). Crankcase oil drains were taken from each car at oilchange intervals of about 3,000 miles of service and these drains combined. A 30-cc. sample of each of the combined drains was mixed with 1% by weight of the dispersant additive to be tested and 2% by weight of water. This mixture then was homogenized, placed in a 100-cc. graduated cone-shaped centrifuge tube and centrifuged for two hours at 1500 rpm. The various dispersants were evaluated by noting the volume of deposited sediment in terms of cubic centimeters and also the turbidity of the supernatant oil layer. It is apparent that the more effective dispersants will give test results which show a minimum of deposited sediment and a relatively hazy supernatant oil layer.

The clarity of the supernatant oil layer was determined by the amount of light transmitted through it from a 3-volt, 0.75 watt incandescent bulb.

The results of these tests are shown in Table I.

TAB LE I Centimeters of Sediment Turbidity of Oil Layer None Prior art Product of Example 83- Product of Example 5- Product of Example 3. Product of Example 1- Product of Example 2 Product of Example 6 Clear-translucent.

o. Opaque.

s q pppp CHI-c0030,

Do. Heavy haze. Do.

The dispersant properties of the compositions of this invention may be illustrated also by the results of an oxidation-dispersancy test which is useful as a screening test for determining the effectiveness of the dispersant additive under light-duty service conditions. In this test a 350-cc. sample of a lubricating oil containing the dispersant additive is placed in a 2 x 15" borosilicate tube. A 1%" x 5%" SAE 1020 steel panel is immersed in the oil. The sample then is heated at 300 F. for 48 hours while air is bubbled through the oil at the rate of 10 liters per hour. The oxidized sample is cooled to F., homogenized, allowed to stand at room temperature for 24 hours and then filtered through two layers of No. 1 Whatman filter paper at 20 mm. Hg pressure. The weight of the precipitate, washed with naphtha and dried, is taken as a measure of the effectiveness of the dispersant additive, i.e., the greater this weight of precipitate the less effective the dispersant.

Two modifications of the above procedure may be employed; both make the test more severe: one consists of extending the test from 48 hours to 96 hours, and the other involves adding 0.5 of water, based on the weight of the test sample, to the oxidized oil before homogenization.

The lubricating oil employed in this test (Table II) was a Mid-Continent conventionally refined petroleum oil having a viscosity of about 200 SUS/ 100 F., and

29 containing 0.001% by weight of iron naphthenate (to promote oxidation).

TAB LE II Oxidation-Dispersance Test Result, mg. of deposit 100 ml. of oil tested Additive Tested (1.5% by weight of diluentlree chemical) None .s 144 o- 275 (b) Dos l, 000 (a, b) Prior art product of Example 83- 738 Prior art product of Example 84- 1,060 (b) Prior art product of Example 85- Product of Example 1-. Product of Example 2.. Product of Example 3.- Product of Example 4..

Product of Example 10 Product of Example 11- Product of Example 12. Product of Example 13. Product of Example 14. Product of Example 14- Product of Example l4 Product of Example l5 Product of Example 16 Product of Example 38 Product of Example 38 Product of Example 4L Product of Example 4L Product of Example 40 Product of Example 40. Product of Example 35 Product of Example 47-.. Product of Example 44 Product of Example 49 Modification (a): 96 hours testing. Modification (b): 0.5% of water used in the test.

Further illustration of the usefulness of the products of this invention as dispersants in motor oils was gained from a modified version of the CRC-EX-3 Engine Test. This test is recognized in the field as an important test by which lubricants can be evaluated for use under light duty service conditions. In this particular test the lubricant is used in the crankcase of a 1954 6-cylinder Chevrolet Powerglide engine for 144 hours under recurring cycling conditions, each cycle consisting of:

2 hours at an engine speed of 500 :25 r.p.m. under zero load at an oil sump temperature of 100125 F.; air-fuel ratio of 10:1;

2 hours at an engine speed of 2500 :25 r.p.m. under a load of 40 brake-horsepower at an oil sump temperature of 160-l70 F.; air-fuel ratio of 16:1;

2 hours at an engine speed of 2500 :25 rpm. under a load of 40 brake-horsepower at an oil sump temperature of 240-250 F.; air-fuel ratio of 16:1.

After completion of the test, the engine is dismantled and various parts of the engine are examined for engine deposits. The lubricant dispersant addition agent is then rated according to 1) the extent of piston ring-filling, (2) the amount of sludge formed in the engine (on a scale of 80*0, 80 being indicative of no sludge and 0 being indicative of extremely heavy sludge), and (3) the total amount of engine deposits, i.e., sludge and varnish, formed in the engine (on a scale of 100-0, 100 being indicative of no deposits and 0 being indicative of extremely heavy deposits). The results are summarized in Table III.

TAB LE III 1 Ordinarily this test lasts for 96 hours.

What is claimed is:

1. A composition comprising a major proportion of a lubricating oil and a minor proportion sufficient to impart detergency thereto of an oil-soluble acylated nitrogen compound characterized by the presence within its structure of (A) a substantially saturated hydrocarbonsubstituted polar group selected from the class consisting of acyl, acylimidoyl, and acyloXy radicals wherein the substantially saturated hydrocarbon substituent contains at least about 50 aliphatic carbon atoms and (B) a nitrogen-containing group characterized by a nitrogen atom attached directly to said polar radical.

2. The composition of claim 1 wherein the hydrocarbon substituent contains at least about 25 aliphatic carbon atoms per each polar radical.

3. The composition of claim 1 wherein the hydrocarbon substituent is a polymer of butene.

4. The composition of claim 1 wherein the hydrocarbon substituent is a polyisobutene having a molecular Weight within the range from about 700 to about 100,000.

5. The composition of claim 1 wherein the nitrogencontaining group has the formula wherein R and R are selected from the group consisting of hydrogen, hydrocarbon, amino-substituted hydrocarbon, hydroxy-substituted hydrocarbon, alkoxy-substituted hydrocarbon, amino, carbamyl, thiocaribamyl, guanyl, and acylimidoyl radicals.

6. A composition comprising a major proportion of a lubricating oil and a minor proportion sufficient to impart detergency thereto of an oil-soluble acylated nitrogen compound characterized by the presence within its structure of (A) a substantially saturated hydrocarbonsubstituted succinic radical selected from the class consisting of succinoyl, succinoylimidoyl, and succinoyloxy radicals and having at least about 50 aliphatic carbon atoms in the substantially saturated hydrocarbon substituent and (B) an amino group characterized by a nitrogen atom attached directly to said succinic radical.

7. A composition comprising a major proportion of a lubricating oil and a minor proportion sufficient to impart detergency thereto of an oil-soluble acylated nitrogen compound characterized by the presence within its structure of (A) an olefin polymer-substituted succinic radical selected from the class consisting of succinoyl, succinimidoyl, and succinoyloxy radicals, said olefin polymer having a molecular weight within the range from about 700 to about 50,000 and being a polymer of a 1- mono-olefin having from 2, to about 8 aliphatic carbon atoms, and (B) a nitrogen-containing group characterized by at least one nitrogen atom attached directly to said succinic radical, said nitrogen-containing group being derived from an alkylene amine.

8. A composition comprising a major proportion of a lubricating oil and a minor proportion sufficient to impart detergency thereto of an oil-soluble acylated nitrogen-containing composition prepared by the process comprising rcacting at a temperature of from about C. and up to the decomposition point a high molecular weight acid-producing compound characterized by the presence within its structure of a high molecular weight oil-solubiliz'ing substantially saturated group having at least about 50 aliphatic carbon atoms and at least one acid-producing group having the structural configuration 2 moles, per equivalent of said acid producing compound, of a nitrogen-containing compound characterized by the 31 presence within its structure of at least one radical having the structural configuration 1I]' H 9. The composition of claim 8 wherein the high molecular weight acid-producing compound is selected from the group consisting of substituted succinic acids having the structural formula RC|1HCOOH CH2-COOH and substituted succinic anhydrides having the structural formula RCHCO o CHz-GO in which structural formulas R is a substantially saturated radical having at least about 50 aliphatic carbon atoms and a butene polymer group.

10. The composition of claim 8 wherein the nitrogencontaining compound is characterized by the structural formula RNH Iii!

in which structural formula R and R" are selected from the group consisting of hydrogen, hydrocarbon, amino-su'bstituted hydrocarbon, alkoxy-substitut ed hydrocarbon, amino, carbamyl, thiocarbamyl, guanyl, and acyl-imidoyl radicals.

11. The composition of claim 8 wherein the nitrogencontaining compound is a polyethylene polyamine.

12. A lubricating composition comprising a major proportion of a lubricating oil and a minor proportion, sufficient to impart detergency thereto, of an amide having the structural formula wherein x is at least 1, R is a substantially saturated hydrocarbon group having at least about 50 aliphatic carbon atoms and at least about 25 aliphatic carbon atoms for each unit of x, and NR' is selected from the class consisting of (A) radicals derived from an alkylene polyamine by the removal of a hydrogen atom from an amino group and (B) radicals derived from an alkylene polyamine by the removal of a hydrogen atom from an amino group and characterized by the presence, on the nitrogen atom of at least one additional amino group, of a complex substituent having the formula 13. A lubricating composition comprising a major proportion of a lubricating oil and a minor proportion, sufficient to impart detergency thereto, of an amide having the structural formula wherein x is at least 1, R is a substantially saturated hydrocarbon group having at least about 50 aliphatic carbon atoms and at least about 25 aliphatic carbon atoms for each unit of x, and NR is selected from the class consisting of (A) radicals derived from an ethylene polyamine by the removal of a hydrogen atom from an amino group and (B) radicals derived from an ethylene polyamine by the removal of a hydrogen atom from an amino group and characterized by the presence, on the nitrogen atom of at least one additional amino group, of a complex substituent having the formula 14. The lubricating composition of claim 12 wherein R of the structural formula is a polyisobutene group having a molecular weight of from about 750 to 5000, x is about 1, and NR' is derived from an ethylene polyamine having from 2 to 8 amino groups by the removal of a hydrogen atom from an amino group and characterized by the presence, on the nitrogen atom of at least one additional amino group, of a complex substitutent having the formula 15. The composition of claim 8 wherein the oil-soluble acylated nitrogen-containing composition is prepared by a process which comprises reacting at a temperature within the range of from about C. to about 250 C. a substantially saturated hydrocarbon substituted succinicacid-proclucing compound having at least about 50 aliphatic carbon atoms in the substantially saturated hydrocarbon substituent with from about one-half equivalent to about 2 moles, per equivalent of said succinic-acidproducing compound, of an alkylene polyamine.

16. The composition of claim 8 wherein the oil-soluble acylated nitrogen-containing composition is prepared by a process which comprises reacting at a temperature within the range of from about 80 C. to about 250 C. a substantially saturated hydrocarbon substituted succinicacid-producing compound having at least about 50 aliphatic carbon atoms in the substantially saturated hydrocarbon substituent with from about one-half equivalent to about 2 moles per equivalent of said succinic-acidproducing compound, of a polyethylene polyamine.

17. The composition of claim 8 wherein the oil-soluble acylated nitrogen-containing composition is prepared by a process which comprises reacting at a temperature within the range of from about 80 C. to about 250 C. a substantially saturated hydrocarbon substituted succinicacid-producing compound having at least about 50 aliphatic carbon atoms in the substantially saturated hydrocarbon substituent with from about one-half equivalent to about 2 moles, per equivalent of said succinic-acidproducing compound, of a hydroxyalkyl amine.

18. The composition of claim 1 wherein it contains additionally an ash-containing detergent.

References Cited by the Examiner UNITED STATES PATENTS 3,018,250 1/1962 Anderson et al 25251 3,024,195 3/ 1962 Drummond et al. 252-51.5 3,131,150 4/1964 Stuart et al. 252-51.5 X 3,154,560 10/1964 Osuch 252-51.5 X 3,172,892 3/1965 Le Suer et al 25251.5 X 3,219,666 11/1965 Norman et al 2525l.5 X

DANIEL E. WYMAN, Primary Examiner.

P. P. GARVIN, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,272 746 September 13 1966 William M. Le Suer et al.

It is hereby certified'that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 57, for "hours" read hour column 2, line 20, for "provide" read proved column 3, line 16, for "aldehydrp g read aldehydo column 4, lines 17 and I 2 18 for "R C read R C- column 5, line 9, for "High" read Higher line 14, for "Encycylopedia" read Encyclopedia column 10, lines 8 to 10, the right-hand formula should appear as shown below instead of as in the patent column 12 line 9 for "showin" read shown in line 13 for "polyisobuentyl" read polyisobutenyl column 13,

line 24, for "amine" read amide line 40, for "butylenyl" read butenyl column 14, line 31, for "125 C./mm."

read 125 C./30 mm. column 18, line 71, for "temperautre" read temperature column 22, line 45, for "corresponding" read (corresponding column 26, line 18, for "phosphorodithioc" read phosphorodithioic line 49, for "diosopropyl-" read di-isopropyl column 27, line 4, for "dinonylphosphordithioate" read dinonylphosphorodithioate line 24, for "octlphosphorodithioate" read octylphosphorodithioate line 43, for "0.03%" read 0.003%

Signed and sealed this 3rd day of September 1968.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. A COMPOSITION COMPRISING A MAJOR PROPORTION OF A LUBRICATING OIL AND A MINOR PROPORTION SUFFICIENT TO IMPART DETERGENCY THERETO OF AN OIL-SOLUBLE ACYLATED NITROGEN COMPOUND CHARACTERIZED BY THE PRESENCE WITHIN ITS STRUCTURE OF (A) A SUBSTANTIALLY STURATED HYDROCARBONSUBSTITUTED POLAR GROUP SELECTED FROM THE CLASS CONSISTING OF ACYL, ACYLIMIDOYL, AND ACYLOXY RADICALS WHEREIN THE SUBSTANTIALLY STURATED HYDROCARBON STBSTITUENT CONTAINS AT LEAST ABOUT 50 ALIPHATIC CARBON ATOMS AND (B) A NITRO-CONTTAINING GROUP CAHRACTERIZED BY A NITROGEN ATOM ATTACHED DIRECTLY TO SAID POLAR RADICAL.
 5. THE COMPOSITION OF CLAIM 1 WHEREIN THE NITROGENCONTAINING GROUP HAS THE FORMULA 